CN101474898A - Conductive carbon film based on graphene as well as preparation method and application - Google Patents

Conductive carbon film based on graphene as well as preparation method and application Download PDF

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CN101474898A
CN101474898A CNA2009100677073A CN200910067707A CN101474898A CN 101474898 A CN101474898 A CN 101474898A CN A2009100677073 A CNA2009100677073 A CN A2009100677073A CN 200910067707 A CN200910067707 A CN 200910067707A CN 101474898 A CN101474898 A CN 101474898A
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graphene
carbon film
film
conductive carbon
preparation
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陈永胜
黄毅
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Nankai University
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Nankai University
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Priority to US13/144,603 priority patent/US20120012796A1/en
Priority to PCT/CN2010/070203 priority patent/WO2010081423A1/en
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Abstract

The invention relates to a general conductive carbon film based on Graphene and a preparation method. The method for preparing the carbon film mainly comprises the following steps: (1) preparing water-soluble single-layer or multi-layer grapheme; (2) preparing organic soluble single-layer or multi-layer Graphene; (3) shaping the solution (or dispersion liquid) containing the Graphene in 1 or 2 by methods of spin coating, spraying, soaking or casting and the like to prepare a film based on the single-layer or multi-layer Graphene; and (4) chemically reducing or roasting the film obtained in 3 to prepare the carbon film based on the single-layer or multi-layer Graphene. The method can be used for preparing the carbon film on various matrixes such as steel, glass, ceramics, quartz, carbon materials, organic substances and the like.

Description

Conductive carbon film and preparation method and application based on Graphene
Technical field
The present invention relates to the material with carbon element field, particularly a kind of conductive carbon film and preparation method and application based on Graphene (Graphene).The conductive carbon film of this single or multiple lift Graphene has good electric conductivity, thermal conductivity and mechanical property, and production cost is very low, and the preparation method is simple, does not need large complicated instrument, can prepare the sample of various sizes and shape.Has good application prospects in traditional field such as machinery, building, medical treatment and high-tech sectors such as precision instrument, microelectronics and Aero-Space.
Background technology
Carbon is arranged the 6th in the periodic table of elements, be the very general element of distributed in nature.The maximum characteristics of carbon exist numerous allotropes exactly, thereby form from zero dimension (C60), one dimension (CNT), two dimension (Graphene, or title mono-layer graphite) to three-dimensional structure and the diverse material with carbon elements of character such as (diamonds).
Carbon film is the thin-film material that a class is widely used in fields such as machinery, electronics, building and medical treatment.Continuous carbon film material of greatest concern comprises diamond thin (Diamond Film) and amorphous carbon film etc.Several different methods such as diamond thin can pass through preparation, Chinese patent CN 01136303.7 has announced a kind of method by preparing diamond film by using UV photon composite glow discharge chemical gas phase deposition; Chinese patent CN 02104120.2 provides a kind of method with the high orientation of H+ ion etching diamond nuclei preparation (001) diamond thin; Chinese patent CN 89107140.7) invented a kind of method that adopts the arc discharge chemical vapor deposition diamond film.Generally speaking, the preparation of diamond thin need be carried out under high temperature (as 800-100 ℃, even higher) high pressure, and be difficult to the large-area evenly smooth diamond thin of preparation, its production cost height, productive rate is lower, has limited its application in a lot of fields.Amorphous carbon film is a kind of thin-film material that grows up the seventies in 20th century, owing to have structure similar and character to diamond thin, so the DLC film that is otherwise known as (Diamond-Like Carbon Films).1971, (Journal of AppliedPhysics, 1971,42,2953) reported first such as American Studies personnel Aisenberg particle beams deposition (Ion Beam Deposition) preparation method of amorphous carbon film; Nineteen eighty-two, Craig etc. (Thin Solid Film, 1982,97,345) adopt magnetron sputtering (MagnetronSputtering) method to prepare amorphous carbon film.Developed the method that laser plasma deposition (Laser PlasmaDeposition), glow discharge (Glow Discharge), arc deposited (Arc Deposion) etc. prepare amorphous carbon film afterwards again.Chinese patent CN 97118531.X has announced that a kind of using plasma chemical meteorology deposition prepares the method for amorphous carbon film; Chinese patent CN 97103251.3 has announced a kind of method and device that adopts vacuum plasma to prepare large area amorphous attitude carbon film.
As a whole, diamond thin and amorphous carbon film mostly adopt specific process such as chemical vapor deposition (CVD) or physical vapor deposition (PVD) and instrument to prepare.Will be on various matrixes with this two classes film growth, these matrix materials must be placed in the special instrument, and can bear the specific conditions such as electric arc, plasma, high temperature, high pressure or high vacuum of vapour deposition when preparing carbon film, therefore, be difficult to adopt this method to go up the preparation carbon film at the matrix (as polymer) of less stable.In addition, be limited to the capacity of instrument cavity, prepare carbon film on the matrix that is difficult to be implemented in large scale or have complicated shape.
Graphene is the novel two-dimensional nano material with carbon element that a class is made up of one deck carbon atom, is the thinnest in the world present two-dimensional material.Find that at present the intensity of this material is the highest in the known materials, its conductive capability and current carrying density all surpass best SWCN at present; Its good quantum hall effect (Quantum Hall Effect) has also obtained proof; Film and the composite thereof that obtains based on this material has good mechanical performance recently.This new material is expected to start a new revolution in fields such as microelectronics, machinery and medical science.It comprises memory cell, triode based on magnetic at the magnetic quantum device, conduction and reinforced composite, and aspects such as energy and material have important application prospects.As be expected to replace silicon chip, as efficient transistor, thereby increase substantially the performance etc. of computer.With the native graphite is raw material, by the preparation in enormous quantities of chemical method realization Graphene, low price; In water and organic solvent, have good dissolubility through the later mono-layer graphite of chemistry functional, help it and evenly disperse and processing and forming; And, adopting the method for electronation or roasting, functional group or defective that can all or part of elimination Graphene be recovered the structure and the performance (comprising electric conductivity, thermal conductivity and mechanical property etc.) of Graphene.
Summary of the invention
The purpose of this invention is to provide a kind of conductive carbon film and preparation method and application based on Graphene.The present invention is to be raw material with graphite or other material with carbon elements, prepare water miscible single or multiple lift Graphene by chemical method, method by organic functional then, prepare organic soluble single or multiple lift Graphene, again by methods such as spin coating, spraying, immersions in various substrate material surface moulding, after electronation or roasting can obtain the general carbon film based on the single or multiple lift Graphene.Compare with amorphous carbon film with the diamond thin of insulation, have good electric conductivity based on the carbon film of Graphene.This carbon film also has good thermal conductivity and mechanical property simultaneously; And its production cost is very low, and the preparation method is simple, low price, and light weight has the solution handlability, and processing and forming is good, does not need large complicated instrument; The sample that can prepare various sizes and shape.Carbon film based on the single or multiple lift Graphene has good application prospects in traditional field such as machinery, building, medical treatment and high-tech sectors such as precision instrument, microelectronics and Aero-Space.
General conductive carbon film provided by the invention is to be raw material with the Graphene, applies film forming at device surface by the method that applies on substrate or directly.Wherein the thickness of single-layer graphene film is 0.34-1.4nm; The thickness of multi-layer graphene film is 0.7-7nm.The electrical conductivity of this carbon film is 1 * 10 -4-1 * 10 4S/cm.This grapheme material has water or organic solvent solubility, and therefore available general solution methods is handled system film etc., has great convenience.
The preparation method of a kind of general conductive carbon film based on Graphene provided by the invention comprises the steps:
1) utilizes graphite or other material with carbon elements, have water miscible single or multiple lift Graphene by the chemical oxidation method preparation;
2), prepare organic soluble single or multiple lift Graphene solution with the method for water miscible single or multiple lift Graphene by organic functional;
3) with step 1) or 2) the single or multiple lift Graphene of described solution-processible, dries the back and obtains film based on the single or multiple lift Graphene in the substrate material surface moulding by the method that applies;
4) film that is carried on the matrix that obtains in the step 3) can be obtained carbon film based on the single or multiple lift Graphene through electronation or roasting.
The preparation method of a kind of general conductive carbon film based on Graphene provided by the invention comprises the steps:
1) single-layer graphene is soluble in water, ultrasonic wave is handled, and it is dissolved fully; Maybe will be dissolved in the organic solvent through the single or multiple lift Graphene of organic functional, ultrasonic wave is handled, and it is dissolved fully.The concentration range of Graphene solution is between 0.1-10mg/mL.
2) method that described Graphene solution place is passed through to apply is at the substrate material surface coating molding, and normal temperature is placed 48-72h down, dries the film of back acquisition based on the single or multiple lift Graphene.
3) film with load on the matrix material reduces with reducing agent; Or the film of the load of reducing in 400-1100 ℃ of following roasting 1-5h, can obtain the matrix that surface-coated has single-layer graphene or multi-layer graphene conductive carbon film under nitrogen protection.
The method of described coating is immersion, spin coating, spraying or casting.Described organic functional reagent is methyl diphenylene diisocyanate.
Described matrix material is a kind of in iron and steel, glass, pottery, quartz, material with carbon element or the organic matter material, and the organic matter matrix material that wherein is used for the load carbon film is a kind of of polyurethane, polyacrylate, polyester, polyamide, ABS, polyethylene, polypropylene, Merlon, polyvinyl chloride, polyimides, epoxy resin, phenolic resins or rubber.
Described reducing agent is at least a in hydrazine, hydrazine hydrate, Dimethylhydrazine and/or the sodium borohydride.Preferred hydrazine hydrate, sodium borohydride.
Described organic solvent is acetone, N, N-dimethyl formamide (DMF), ethanol, benzene, dichloro-benzenes, oxolane, acetonitrile etc.
The present invention can be applicable to traditional field and high-tech sector devices such as precision instrument, microelectronics and Aero-Space such as machinery, building, medical treatment.
The present invention has following advantage:
1) single or multiple lift Graphene water soluble provided by the invention or organic solvent are implemented in various materials or body surface easily and form uniform carbon film; Compare methods such as traditional chemical meteorology deposition, plasma sputtering, this method technology is simple, with low cost, the equipment input is little, also can be applicable to the product with complicated shape.
2) Graphene has good electric conductivity, and formed carbon film has favorable conductive, antistatic effect.
3) Graphene has the best mechanical property of known materials, makes carbon film provided by the invention have higher intensity and modulus, might use under particular surroundings such as building, machinery and Aero-Space.
4) because mono-layer graphite has good heat conductivility, make carbon film provided by the invention have advantages such as the heat radiation of being easy to, be expected to obtain to use in fields such as precision instrument and microelectronics.
5) when the thickness of Graphene carbon film during, have good light transmission, can obtain transparent conductive film less than 10 nanometers.
The specific embodiment
Below by embodiment the present invention is specifically described; present embodiment only is used for that the present invention is further illustrated; can not be interpreted as limiting the scope of the invention; those skilled in the art makes some nonessential improvement and adjustment according to the content of the invention described above, all belongs to protection domain of the present invention.
Embodiment 1: based on the general conductive carbon film of single-layer graphene
Adopt chemical oxidation method to prepare single-layer graphene.10g graphite and 7g sodium nitrate (analyzing pure) are added in the flask, add the 500mL concentrated sulfuric acid (analyzing pure) then.In ice-water bath, slowly add 40g potassium permanganate while stirring afterwards, the joining day is controlled at 2h, keeps 2h to make it to be cooled to room temperature afterwards.Stirring at room 10 days, reaction solution fades to green earlier, and then becomes dark-brown, and it is brown to become brick at last, and it is thick to become sticky.Reaction solution is slowly joined in the dilute sulfuric acid of 1000mL 5wt%, the joining day is controlled at 2h, keeps stirring, and temperature is controlled at 98 ℃.Reactant liquor continues to stir 2h under this temperature again, is cooled to 60 ℃ then.Add 30mL hydrogen peroxide (30% aqueous solution), keep 2h, reduce to room temperature afterwards, stir 2h at 60 ℃.For removing the ion that oxidizing substance brings, especially manganese ion, use centrifugation method to carry out removal of impurities reaction solution, centrifugal number of times is 15 times: centrifugal 10min under 4000rpm, remove supernatant, the mixed liquor that adds the 2L 3wt% concentrated sulfuric acid/0.5wt% hydrogen peroxide, strong agitation and under 200W the ultrasonic 30min of water-bath, repeat 15 times.Use the hydrochloric acid of 3wt% to repeat above-mentioned steps 3 times afterwards, use distilled water to repeat 1 time.Afterwards reactant liquor is transferred in the acetone, removed remaining acid.Final drying obtains the single-layer graphene of functionalization, and productive rate is 70%.The single-layer graphene of this functionalization contains organo-functional groups such as hydroxyl, carboxyl and epoxy bond, and the mass percent of functional group is 20%.
The 1g single-layer graphene is added in the entry, handled 30 minutes, it is dissolved fully through the 500W ultrasonic wave.The mono-layer graphite aqueous solution (is placed 48h, glass plate is placed on soaks 24h in the pure hydrazine solution then, the single-layer graphene conductive carbon film after obtaining reducing at the glass substrate that cleaned by the method for spraying under 10 * 10cm) surface filmings, normal temperature.The method of mono-layer graphite aqueous solution by spin-coating respectively on steel plate, iron plate, potsherd, quartz plate, organic matter film (comprising polyurethane, polyester, polyamide, ABS, polyethylene, polypropylene, Merlon, polyvinyl chloride, polyimides, epoxy resin, phenolic resins or rubber etc.) matrix, can be obtained single-layer graphene conductive carbon film after the reduction by same method.The characterization result of the carbon film of this method preparation is listed in the table 1.
Table 1
Matrix material The thickness of single-layer graphene carbon film Outward appearance Situation is rubbed in scratch resistance Electrical conductivity (S/cm)
Glass plate 1μm Grey, translucent Well 5×10 -1
Steel plate 1μm Grey, translucent Well The matrix conduction
Iron plate 1μm Grey, translucent Well The matrix conduction
Quartz plate 1μm Grey, translucent Well 5×10 -1
Potsherd 10μm Grey, translucent Well 6×10 -1
Polyurethane film 10μm Grey, translucent Well 6×10 -1
Polyester film 10μm Grey, translucent Well 6×10 -1
PA membrane 10μm Grey, translucent Well 6×10 -1
The ABS film 10μm Grey, translucent Well 6×10 -1
Polyethylene film 10μm Grey, translucent Well 6×10 -1
Polypropylene screen 10μm Grey, translucent Well 6×10 -1
Polychloroethylene film 100μm Black, opaque Well 6×10 -1
Polyimide film 100μm Black, opaque Well 6×10 -1
Epoxy sheet 100μm Black, opaque Well 6×10 -1
The phenolic resins sheet 100μm Black, opaque Well 6×10 -1
Sheet rubber 100μm Black, opaque Well 6×10 -1
Embodiment 2: based on the transparent conductive carbon film of single-layer graphene
Method according to embodiment 1 prepares single-layer graphene.The 1g single-layer graphene is added in the entry, handled 30 minutes, it is dissolved fully through the 500W ultrasonic wave.
The mono-layer graphite aqueous solution (is placed 48h by the method for spin-coating at the quartz plate that cleaned under 15 * 15 * 3mm) surface filmings, normal temperature; The single-layer graphene film that will load on then on the quartz plate is placed in the closed container, with the stifling 24h of hydrazine hydrate (98%, Alfa Aesar) steam; Obtain the single-layer graphene film of hydrazine steam reduction.Single-layer graphene film with the hydrazine steam reduction is positioned in the tube furnace, under nitrogen protection, in 400 ℃ of following roasting 3h, obtains the single-layer graphene carbon film of electrically conducting transparent; In addition, with the single-layer graphene film of hydrazine steam reduction in vacuum (10 -5Torr) under,, obtain the single-layer graphene carbon film of electrically conducting transparent in 1000 ℃ of following roasting 1h.The characterization result of the carbon film of this method preparation is listed in the table 2.
Table 2
Sintering temperature The thickness of single-layer graphene carbon film Outward appearance Visible light transmissivity (%) Electrical conductivity (S/cm)
400℃ 5nm Colourless, transparent 90 2×102
400℃ 10nm Colourless, translucent 60 2×10 2
400℃ 20nm Colourless, translucent 40 3×10 2
1000℃ 20nm Colourless, translucent 40 2×10 3
Embodiment 3: based on the general conductive carbon film of multi-layer graphene
Method according to bibliographical information prepares multi-layer graphene (Carbon, 2004,42,2929), and resulting product obtains the mixture of 2-5 layers Graphene through centrifugation.The 1g multi-layer graphene is added in the entry, handled 60 minutes, it is dissolved fully through the 500W ultrasonic wave.Add the 0.5g sodium borohydride, stir, react 2h down at 80 ℃, solution has obtained the Graphene dispersion liquid after the reduction by the brown black that changes into.
Above-mentioned Graphene dispersion liquid is passed through the method for cast at the glass substrate that cleaned (10 * 10cm) surface filmings; normal temperature is placed 48h down; to be carried on graphene film on the glass substrate then under nitrogen protection; in 400 ℃ of following roasting 3h; the multi-layer graphene carbon film that obtains conducting electricity, its electrical conductivity are 2 * 10 2S/cm.
Embodiment 4: be coated with the material based on the conductive carbon film of single-layer graphene
Method according to embodiment 1 prepares single-layer graphene.The 1g single-layer graphene is added in the entry, handled 30 minutes, it is dissolved fully through the 500W ultrasonic wave.
Silicon nitride ceramics is soaked 10min in the mono-layer graphite aqueous solution, place 48h after the taking-up at normal temperatures; Place it in then in the closed container, with the stifling 24h of hydrazine hydrate (80%, Alfa Aesar) steam; Under nitrogen protection,, obtain the silicon nitride ceramics that surface-coated has the single-layer graphene conductive carbon film at last in 400 ℃ of following roasting 2h.
Profit uses the same method, and preparing surface-coated has materials such as the aluminium oxide ceramics of single-layer graphene conductive carbon film, steel alloy, tool steel, the pig iron, quartz, glass.
Being coated with based on the material of the conductive carbon film of single-layer graphene of this method preparation listed in the table 3.
Table 3
Matrix material Coat thickness (nm) The coat outward appearance Situation is rubbed in scratch resistance Electrical conductivity (S/cm)
Silicon nitride ceramics 5 Colourless, transparent Well 2×10 2
Aluminium oxide ceramics 5 Colourless, transparent Well The matrix conduction
Steel alloy 20CrMnSi 4 Colourless, transparent Well The matrix conduction
Tool steel SKH52 4 Colourless, transparent Well The matrix conduction
The pig iron 4 Colourless, transparent Well The matrix conduction
Quartz plate 5 Colourless, transparent Well 2×10 2
Sheet glass 5 Colourless, transparent Well 2×10 2
Embodiment 5: based on the general conductive carbon film of organic soluble single-layer graphene
Method according to embodiment 1 prepares single-layer graphene.The 0.2g single-layer graphene is added in the there-necked flask, add the DMF that 300mL dewaters through distillation, handled 40 minutes, it is dissolved fully through the 500W ultrasonic wave; Logical nitrogen protection adds 0.4g methyl diphenylene diisocyanate (Methylenediphenyl Diisocyanate is called for short MDI), nitrogen protection, and stirring at room 5 days is passed through high speed centrifugation (10000 rev/mins) again, filters, and vacuum drying.Obtain the single-layer graphene of MDI functionalization, productive rate 75%.
The single-layer graphene of 0.2g MDI functionalization is added 200mL N, in the dinethylformamide (DMF), handled 40 minutes, it is dissolved fully through the 500W ultrasonic wave; (place 48h under 5 * 5cm) surface filmings, normal temperature by the method for spin-coating at the glass plate that cleaned then; The single-layer graphene film that will load on then on the glass plate is placed in the closed container, with the stifling 24h of hydrazine hydrate (80%, Alfa Aesar) steam; Obtain the single-layer graphene film of hydrazine steam reduction; At last it is positioned in the tube furnace, under nitrogen protection,, obtains based on organic soluble single-layer graphene carbon film in 400 ℃ of following roasting 3h.The thickness of this film is 100nm, and electrical conductivity is 3 * 10 2S/cm.
Embodiment 6: based on the general conductive carbon film of organic soluble multi-layer graphene
Method according to bibliographical information prepares multi-layer graphene (Carbon, 2004,42,2929), and resulting product obtains the mixture of 2-5 layers Graphene through centrifugation.The 1g multi-layer graphene is added in the entry, handled 60 minutes, it is dissolved fully through the 500W ultrasonic wave.The 0.2g multi-layer graphene is added in the there-necked flask, add the DMF that 300mL dewaters through distillation, through 500W ultrasonic wave (Kunshan Ultrasonic Instruments Co., Ltd., model: KQ-500DB) handled 40 minutes, it is dissolved fully; Logical nitrogen protection adds 0.3g toluene di-isocyanate(TDI) (Toluene Diisocyanate is called for short TDI), nitrogen protection, and stirring at room 5 days is passed through high speed centrifugation (10000 rev/mins) again, filters, and vacuum drying.Obtain the multi-layer graphene of TDI functionalization, productive rate 70%.
The single-layer graphene of 0.2g TDI functionalization is added in the 200mL acetone, through 500W ultrasonic wave (Kunshan Ultrasonic Instruments Co., Ltd., model: KQ-500DB) handled 40 minutes, it is dissolved fully; (30 * 30 * 3mm) soak 10min to quartz plate in the acetone soln of multi-layer graphene, place 12h after the taking-up at normal temperatures then; Place it in then in the closed container, with the stifling 24h of hydrazine hydrate (80%, Alfa Aesar) steam; At last in vacuum (10 -5Torr) under, in 1100 ℃ of following roasting 1h, obtain the multi-layer graphene carbon film, its thickness is 10nm, and electrical conductivity is 5 * 10 4S/cm.

Claims (10)

1, a kind of conductive carbon film, it is characterized in that it is is raw material with the Graphene, apply film forming at device surface by the method that applies on substrate or directly, wherein the thickness of single-layer graphene film is 0.34-1.4nm, the thickness of multi-layer graphene film is 0.7-7nm, and the electrical conductivity of carbon film is 1 * 10 -4-1 * 10 4S/cm.
2,, it is characterized in that the number of plies of described multi-layer graphene is 2-5 layers according to the described conductive carbon film of claim 1.
3, a kind of preparation method of the conductive carbon film based on Graphene is characterized in that comprising the steps:
1) utilize graphite or other material with carbon elements, the method by chemical oxidation obtains to have water miscible single or multiple lift Graphene;
2), prepare organic soluble single or multiple lift Graphene solution with the method for water miscible single or multiple lift Graphene by organic functional;
3) with step 1) or 2) the single or multiple lift Graphene of described solution-processible, dries the back and obtains film based on the single or multiple lift Graphene in the substrate material surface moulding by the method that applies;
4) film that is carried on the matrix that obtains in the step 3) can be obtained carbon film based on the single or multiple lift Graphene through electronation or roasting.
4, a kind of preparation method of the conductive carbon film based on Graphene is characterized in that comprising the steps:
1) single-layer graphene is soluble in water, ultrasonic wave is handled, and it is dissolved fully; Maybe will be dissolved in the organic solvent through the single or multiple lift Graphene of organic functional, ultrasonic wave is handled, and it is dissolved fully.The concentration range of Graphene solution is between 0.1-10mg/mL.
2) method that described Graphene solution place is passed through to apply is at the substrate material surface coating molding, and normal temperature is placed 48-72h down, dries the film of back acquisition based on the single or multiple lift Graphene.
3) film with load on the matrix material reduces with chemical reducing agent; Or the film of the load of reducing in 400-1100 ℃ of following roasting 1-4h, can obtain the matrix that surface-coated has single-layer graphene or multi-layer graphene conductive carbon film under nitrogen protection.
5, according to the preparation method of the described conductive carbon film of claim 4, the method that it is characterized in that described coating is immersion, spin coating, spraying or casting.
6,, it is characterized in that described matrix material is a kind of in iron and steel, glass, pottery, quartz, material with carbon element or the organic matter material according to the preparation method of the described conductive carbon film of claim 4.
7,, it is characterized in that described organic matter matrix material is a kind of in polyurethane, polyacrylate, polyester, polyamide, ABS, polyethylene, polypropylene, Merlon, polyvinyl chloride, polyimides, epoxy resin, phenolic resins or the rubber according to the preparation method of the described conductive carbon film of claim 4.
8,, it is characterized in that described reducing agent is at least a in hydrazine, hydrazine hydrate, Dimethylhydrazine and/or the sodium borohydride according to the preparation method of the described conductive carbon film of claim 4.
9,, it is characterized in that described reducing agent is hydrazine hydrate or sodium borohydride according to the preparation method of the described conductive carbon film of claim 4.
10, the application of the described conductive carbon film of claim 1 in machinery, building, medical field and precision instrument, microelectronics and field of aerospace technology.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
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US9832818B2 (en) 2011-09-30 2017-11-28 Ppg Industries Ohio, Inc. Resistive heating coatings containing graphenic carbon particles
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US9133545B2 (en) 2013-10-23 2015-09-15 Corning Incorporated Glass-ceramics substrates for graphene growth
WO2015132764A1 (en) * 2014-03-06 2015-09-11 True 2 Materials Pte Ltd Method for manufacture of films and foams
JP6688225B2 (en) * 2014-04-04 2020-04-28 シグニファイ ホールディング ビー ヴィＳｉｇｎｉｆｙ Ｈｏｌｄｉｎｇ Ｂ．Ｖ． Method for manufacturing graphene layer
WO2016070068A1 (en) * 2014-10-31 2016-05-06 Ppg Industries Ohio, Inc. Resistive heating coatings containing graphene carbon particles and use of such coatings for low energy curing
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US10717653B2 (en) * 2017-11-08 2020-07-21 Vaon, Llc Graphene production by the thermal release of intrinsic carbon
US11332830B2 (en) 2017-11-15 2022-05-17 Global Graphene Group, Inc. Functionalized graphene-mediated metallization of polymer article
US20190144621A1 (en) * 2017-11-15 2019-05-16 Nanotek Instruments, Inc. Graphene-Mediated Metal-Plated Polymer Article and Production Method
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100117570A (en) * 2008-01-03 2010-11-03 내셔널 유니버시티 오브 싱가포르 Functionalised graphene oxide
WO2009123771A2 (en) * 2008-02-05 2009-10-08 Crain John M Coatings containing functionalized graphene sheets and articles coated therewith
US8182917B2 (en) * 2008-03-20 2012-05-22 The United States Of America, As Represented By The Secretary Of The Navy Reduced graphene oxide film
TW201012749A (en) * 2008-08-19 2010-04-01 Univ Rice William M Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom
CN101372553A (en) * 2008-10-24 2009-02-25 南开大学 Functionalized single layer graphite and polyurethane photo-induced shape memory composite material and preparation thereof
CN101474898A (en) * 2009-01-16 2009-07-08 南开大学 Conductive carbon film based on graphene as well as preparation method and application
CN101474899A (en) * 2009-01-16 2009-07-08 南开大学 Grapheme-organic material layered assembling film and preparation method thereof
CN101474897A (en) * 2009-01-16 2009-07-08 南开大学 Grapheme-organic material layered assembling film and preparation method thereof

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